CN106281287A - A kind of feature of environmental protection free-floride cleanup additive and preparation method - Google Patents
A kind of feature of environmental protection free-floride cleanup additive and preparation method Download PDFInfo
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- CN106281287A CN106281287A CN201610561811.8A CN201610561811A CN106281287A CN 106281287 A CN106281287 A CN 106281287A CN 201610561811 A CN201610561811 A CN 201610561811A CN 106281287 A CN106281287 A CN 106281287A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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Abstract
The present invention relates to a kind of feature of environmental protection free-floride cleanup additive, be 10～the solvent of the cationic surfactant of the nonionic surfactant of the anion surfactant of 35%, 5～10%, 1～5%, 10～30% including mass percent, remaining is water.Not fluorine-containing surfactant, low cost in the cleanup additive of the present invention, biological degradability is good；Additionally, the cleanup additive concentration of the present invention is low, during 0.5wt ‰, surface tension is less than 26mN/m, is less than 0.05mN/m with the interfacial tension of kerosene, and cost performance is high, can reduce the chemical substance discharge capacity to environment.
Description
Technical field
The present invention relates to cleanup additive field, be specifically related to a kind of free-floride for Oil/gas Well, low surface tension, low interface are opened
Feature of environmental protection free-floride cleanup additive of power and preparation method thereof.
Background technology
Reduce hydraulic fluid surface tension when Oil/gas Well cleanup additive is mainly used in well fracturing, de-plugging and oil-water interfaces are opened
Power.At present, cleanup additive is mainly formed, such as patent ZL by hydrocarbon system surfactant and fluorine-containing surfactant are compounding
200410026257.0, CN 104371702A, CN 104403657A.Fluorine surfactant refers in surfactant hydrocarbon chain
Hydrogen moiety or the surfactant being all replaced by fluorine atoms, its feature is: surface activity is high, can effectively reduce water
Surface tension, and chemical stability is good, resistance to strong acid, highly basic, strong oxidizer and high temperature.But the price mistake of fluorine-containing surfactant
Height, and not easily biological-degradable, thus cause environmental pollution, part perfluorinated surfactant is by international economic cooperation development institution
(OECD) it is defined as being persistently present in environment, there is biological savings property the material to human hazard, therefore, fluorine-containing surfactants
The use of agent is restricted.
In recent years, the most fluorine-containing cleanup additive receives publicity, as used alkyl trimethyl bromine in patent CN 102295919B
Change ammonium or cetylpyridinium bromide makees host, with fatty alcohol-polyoxyethylene ether, double hydroxyethyl laurylamide or glycine betaine for increasing
Strong agent, and add cosolvent and make floride-free acidifying cleanup additive.Wang Hongbiao learns the Daqing Petroleum Institute Master degree candidate of 2009
Degree thesis whole-length " fracturing fluid non-fluorine carbon cleanup additive is studied " uses anion/cation surfactant compound theoretical, preferably goes out surface and opens
Power and relatively low two the cleanup additive formula of interfacial tension: cleanup additive A:12wt% (ABS+LP)+8wt%AES+25% solvent+
55wt% water, cleanup additive B:14wt% (K-12+OS)+6wt%AES+25wt% solvent+55wt% water.The 1wt ‰ of cleanup additive A
Aqueous solution surface tension is 26.4mN/m, is 1.2mN/m with kerosene interfacial tension；The surface of 1wt ‰ aqueous solution of cleanup additive B is opened
Power is 25.0mN/m, is 1.3mN/m with kerosene interfacial tension.In the document that above disclosure is delivered, the interface of floride-free cleanup additive
Performance is the most poor, and the interfacial tension between kerosene is higher.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of feature of environmental protection free-floride cleanup additive and preparation method thereof, there is structure
Simply, the advantages such as simple, cost of manufacture is low are made.
It is an object of the invention to be achieved through the following technical solutions:
A kind of feature of environmental protection free-floride cleanup additive, it is characterised in that include following component by mass percentage:
In preferred embodiments, wherein said anion surfactant, nonionic surfactant and cation
Gross activity thing content in surfactant is 20～50% by mass percentage.
In preferred embodiments, the most double alkyl diphenyl ether disulfonic acid of wherein said anion surfactant choosing
One or more in the group of salt, alkyl alcohol ethoxylates sulfate, alpha-alkene sulfonate and sodium alkyl benzene sulfonate composition.
In preferred embodiments, the long alkyl chains of wherein said pair of p alkylphenylaceticacid selects free C6-
One or more in the group of C10 composition, the long alkyl chains of described alpha-alkene sulfonate selects in the group of free C12-C18 composition
One or more.
In preferred embodiments, wherein said nonionic surfactant selects free alkyl polyglucoside and fatty alcohol polyoxy
Vinyl Ether composition group in one or both.
In preferred embodiments, during the alkyl chain length of wherein said alkyl polyglucoside selects the group of free C6-C10 composition
One or more.
In preferred embodiments, wherein said cationic surfactant select free C12 alkyl trimethyl ammonium bromide,
One or more in the group of C6-10 alkyl trimethyl ammonium chloride and C8-C10 zephiran composition.
In preferred embodiments, wherein said solvent is ethanol or isopropanol.
A kind of preparation method according to above-mentioned feature of environmental protection free-floride cleanup additive, including, to being slowly stirred, (its range of speeds is
Reactor 20-40r/min) adds water and the solvent of aforementioned proportion, and the temperature in reactor is heated to 40-50 DEG C,
Anion surfactant and the nonionic surfactant of aforementioned proportion, (its turn to be mixed is added the most again in reactor
Speed scope is 40-80r/min) uniformly after, add the cationic surfactant of aforementioned proportion, continue stirring (its range of speeds
For 40-80r/min) uniformly, i.e. obtain product.
The present invention has the advantages that relative to prior art
(1) present invention uses Yin/Yang/nonionic surfactant to compound, and particularly selects double type anion table
The double p alkylphenylaceticacid of face activating agent, and by adjusting the lipophilic group structure of anion and cationic surfactant,
Make Yin/Yang surface active agent ion that the arranging density at gas-liquid surface, oil-water interfaces to be increased, thus effectively reduce system
Table/interfacial tension；Nonionic surfactant used in the present invention be mainly used in increasing Yin/Yang surface active agent ion to
Dissolubility in water, and by adjusting its alkane chain structure so that it is with Yin/Yang surface active agent ion at gas-liquid surface, profit
Interface forms mixing and absorption film, reduces the table/interfacial tension of system further；
(2) not fluorine-containing surfactant, low cost in the cleanup additive of the present invention, biological degradability is good；
(3) the cleanup additive concentration of the present invention is low, and during 0.5wt ‰, surface tension is less than 26mN/m, with the interface of kerosene
Tension force is less than 0.05mN/m, and cost performance is high, can reduce the chemical substance discharge capacity to environment.
Detailed description of the invention
A kind of feature of environmental protection free-floride cleanup additive of the embodiment of the present invention, including the anion table that mass percent is 10～35%
The solvent of the cationic surfactant of the nonionic surfactant of face activating agent, 5～10%, 1～5%, 10～30%, remaining
Amount is water.
The preparation method of described feature of environmental protection free-floride cleanup additive: be first initially charged the water of half and whole molten in reactor
Agent, and stir (its range of speeds is 20-40r/min) uniformly, during stirring (its range of speeds is 20-40r/min)
Temperature in reactor is heated to 40-50 DEG C, in stirring (its range of speeds is 40-80r/min) downhill reaction still slowly
Add anion surfactant and nonionic surfactant, treat that solution stirring (its range of speeds is 40-80r/min) is uniform
After, add cationic surfactant and remaining water, continue stirring (its range of speeds is 40-80r/min) uniform, to obtain final product
To product.
The formula of the present invention is described below by concrete example:
Embodiment 1
Anion surfactant is double p alkylphenylaceticacid, and nonionic surfactant is alkyl polyglucoside
(APG), cationic surfactant is C12 alkyl trimethyl ammonium bromide, and its proportioning by mass percentage is as follows:
Described anion surfactant, nonionic surfactant contain with the gross activity thing in cationic surfactant
Amount is 20% by mass percentage.
Preparation method: be initially charged 700kg water and 100kg isopropanol in a kettle., be heated to 40-50 DEG C, under agitation
(its range of speeds is 20r/min) be slowly added to the double p alkylphenylaceticacid 120kg of anion surfactant and non-from
Sub-surface activating agent fatty alcohol-polyoxyethylene ether 60kg, continues stirring (its range of speeds is 40r/min), after system is uniform,
Add cationic surfactant C12 alkyl trimethyl ammonium bromide, continue stirring (its range of speeds is 40r/min) uniform,
I.e. obtain product.When the concentration of this product is 0.5wt ‰, its surface tension having is 25.6mN/m, with kerosene
Interfacial tension is 0.016mN/m.
Embodiment 2
Anion surfactant is alkyl alcohol ethoxylates sulfate (AES), and nonionic surfactant is fat
Polyoxyethylenated alcohol, cationic surfactant is C16 alkyl trimethyl ammonium chloride, and its proportioning by mass percentage is such as
Under:
Described anion surfactant, nonionic surfactant and the gross mass percentage in cationic surfactant
It is 50% than by mass percentage.
Preparation method: be initially charged 350kg water and 150kg isopropanol in a kettle., be heated to 40-50 DEG C, at stirring (its
The range of speeds is 40r/min) under be slowly added to anion surfactant alkyl alcohol ethoxylates sulfate (AES) 350kg
With nonionic surfactant fatty alcohol-polyoxyethylene ether 120kg, continue stirring (its range of speeds is 80r/min), treat system
After Jun Yun, adding cationic surfactant C16 alkyl trimethyl ammonium chloride, (its range of speeds is 80r/ to continue stirring
Min) uniform, i.e. obtain product.When the concentration of this product is 0.5wt ‰, its surface tension having is 25.2mN/m,
It is 0.042mN/m with the interfacial tension of kerosene.
Embodiment 3
Anion surfactant is a-alkene sulfonate (AOS), and nonionic surfactant is alkyl polyglucoside (APG),
Cationic surfactant is C10 alkyl trimethyl ammonium chloride, and its proportioning by mass percentage is as follows:
Described anion surfactant, nonionic surfactant and the gross mass percentage in cationic surfactant
It is 30% than by mass percentage.
Preparation method: be initially charged 500kg water and 200kg isopropanol in a kettle., be heated to 40-50 DEG C, at stirring (its
The range of speeds is 25r/min) under be slowly added to anion surfactant a-alkene sulfonate (AOS) 150kg and nonionic table
Face activating agent alkyl polyglucoside (APG) 140kg, continues stirring (its range of speeds is 50r/min), after system is uniform, adds
Cationic surfactant C10 alkyl trimethyl ammonium chloride, continues stirring (its range of speeds is 50r/min) uniform, i.e. obtains
Product.When the concentration of this product is 0.5wt ‰, surface tension is 25.1mN/m, with the interfacial tension of kerosene is
0.025mN/m。
Embodiment 4
Anion surfactant is SAS (SAS), and nonionic surfactant is aliphatic alcohol polyethenoxy
Ether, cationic surfactant is C8-C10 zephiran, and its proportioning by mass percentage is as follows:
Described anion surfactant, nonionic surfactant and the gross mass percentage in cationic surfactant
It is 40% than by mass percentage.
Preparation method: be initially charged 400kg water and 200kg ethanol in a kettle., be heated to 40-50 DEG C, at stirring (its turn
Speed scope be 30r/min) under be slowly added to anion surfactant SAS (SAS) 250kg and non-ionic surface
Activating agent fatty alcohol-polyoxyethylene ether 120kg, continues stirring (its range of speeds is 60r/min), after system is uniform, adds
Cationic surfactant C8-C10 zephiran, continues stirring (its range of speeds is 60r/min) uniform,
I.e. obtain product.When the concentration of this product is 0.5wt ‰, its surface tension having is 25.3mN/m, with the boundary of kerosene
Surface tension is 0.033mN/m.
Embodiment 5
Anion surfactant is alkyl alcohol ethoxylates sulfate (AES) and alkene sulfonate (AOS), nonionic
Surfactant is fatty alcohol-polyoxyethylene ether, and cationic surfactant is C12-14 alkyl trimethyl ammonium chloride, and it presses matter
The proportioning of amount percentages is as follows:
Described anion surfactant, nonionic surfactant and the gross mass percentage in cationic surfactant
It is 25% than by mass percentage.
Preparation method: be initially charged 600kg water and 150kg isopropanol in a kettle., be heated to 40-50 DEG C, at stirring (its
The range of speeds is 35r/min) under be slowly added to anion surfactant alkyl alcohol ethoxylates sulfate (AES) 50kg,
Alkene sulfonate (AOS) 50kg and nonionic surfactant fatty alcohol-polyoxyethylene ether 100kg, continues stirring (its rotating speed model
Enclose for 70r/min), after system is uniform, add cationic surfactant C12-C14 alkyl trimethyl ammonium chloride 50Kg,
Continue stirring (its range of speeds is 70r/min) uniform, i.e. obtain product.The concentration of this product low for 0.5wt ‰ time, its
The surface tension having is 24.8mN/m, is 0.026mN/m with the interfacial tension of kerosene.
The present invention is not limited to above-mentioned preferred forms, and anyone can show that under the enlightenment of the present invention other are various
The product of form, no matter but in its shape or structure, make any change, every have same as the present application or akin skill
Art scheme, within all falling within protection scope of the present invention.
Claims (9)
1. a feature of environmental protection free-floride cleanup additive, it is characterised in that include following component by mass percentage:
Feature of environmental protection free-floride cleanup additive the most according to claim 1, it is characterised in that: described anion surfactant, non-
Ionic surface active agent is 20～50% with the gross activity thing content in cationic surfactant by mass percentage.
Feature of environmental protection free-floride cleanup additive the most according to claim 1, it is characterised in that: described anion surfactant is selected from
It is made up of double p alkylphenylaceticacid, alkyl alcohol ethoxylates sulfate, alpha-alkene sulfonate and sodium alkyl benzene sulfonate
Group in one or more.
Feature of environmental protection free-floride cleanup additive the most according to claim 3, it is characterised in that: described pair of p alkylphenylaceticacid
Long alkyl chains select one or more in the group of free C6-C10 composition, the long alkyl chains of described alpha-alkene sulfonate selects
One or more in the group of free C12-C18 composition.
Feature of environmental protection free-floride cleanup additive the most according to claim 1, it is characterised in that: described nonionic surfactant is selected from
One or both in the group being made up of alkyl polyglucoside and fatty alcohol-polyoxyethylene ether.
Feature of environmental protection free-floride cleanup additive the most according to claim 5, it is characterised in that: the alkyl chain length choosing of described alkyl polyglucoside
One or more in the group of free C6-C10 composition.
Feature of environmental protection free-floride cleanup additive the most according to claim 1, it is characterised in that: described cationic surfactant is selected from
It is made up of C12 alkyl trimethyl ammonium bromide, C6-10 alkyl trimethyl ammonium chloride and C8-C10 zephiran
One or more in group.
Feature of environmental protection free-floride cleanup additive the most according to claim 1, it is characterised in that: described solvent is ethanol or isopropanol.
9. the preparation method according to the feature of environmental protection free-floride cleanup additive described in any one of claim 1-8, it is characterised in that: bag
Include, in the reactor being slowly stirred, add water and the solvent of aforementioned proportion, and the temperature in reactor is heated to 40-50
DEG C, in reactor, add anion surfactant and the nonionic surfactant of aforementioned proportion the most again, to be mixed all
After even, add the cationic surfactant of aforementioned proportion, continue to stir, i.e. obtain product.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107120103A (en) * | 2017-05-17 | 2017-09-01 | 成都百联油田技术服务有限公司 | A kind of fracture acidizing cleanup additive |
| CN107267132A (en) * | 2017-06-28 | 2017-10-20 | 常州市鑫嘉生物科技有限公司 | A kind of low-adhesion oil well cleanup additive and preparation method thereof |
| WO2018211061A1 (en) * | 2017-05-19 | 2018-11-22 | Rhodia Operations | Additives for eliminating fracturing fluids used for oil extraction |
| CN110776900A (en) * | 2019-11-27 | 2020-02-11 | 陕西延长石油油田化学科技有限责任公司 | High-temperature cleanup additive for oil field and preparation method thereof |
| CN113444508A (en) * | 2021-06-02 | 2021-09-28 | 宁波锋成先进能源材料研究院有限公司 | Cleanup additive and preparation method and application thereof |
| CN114426838A (en) * | 2021-12-16 | 2022-05-03 | 中国石油化工股份有限公司 | Composite synergistic cleanup additive and preparation method thereof |
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| CN105062452A (en) * | 2015-07-15 | 2015-11-18 | 国勘石油技术有限公司 | Demulsification and discharge aiding agent and preparation method thereof as well as treatment method of oil field reservoir |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107120103A (en) * | 2017-05-17 | 2017-09-01 | 成都百联油田技术服务有限公司 | A kind of fracture acidizing cleanup additive |
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| CN107267132A (en) * | 2017-06-28 | 2017-10-20 | 常州市鑫嘉生物科技有限公司 | A kind of low-adhesion oil well cleanup additive and preparation method thereof |
| CN110776900A (en) * | 2019-11-27 | 2020-02-11 | 陕西延长石油油田化学科技有限责任公司 | High-temperature cleanup additive for oil field and preparation method thereof |
| CN113444508A (en) * | 2021-06-02 | 2021-09-28 | 宁波锋成先进能源材料研究院有限公司 | Cleanup additive and preparation method and application thereof |
| CN114426838A (en) * | 2021-12-16 | 2022-05-03 | 中国石油化工股份有限公司 | Composite synergistic cleanup additive and preparation method thereof |
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